CN112777634B - Preparation method of bismuth vanadate with high (010) crystal face exposure ratio - Google Patents

Preparation method of bismuth vanadate with high (010) crystal face exposure ratio Download PDF

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CN112777634B
CN112777634B CN202110141863.0A CN202110141863A CN112777634B CN 112777634 B CN112777634 B CN 112777634B CN 202110141863 A CN202110141863 A CN 202110141863A CN 112777634 B CN112777634 B CN 112777634B
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bismuth vanadate
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陆源
曾海波
张侃
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Nanjing University of Science and Technology
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Abstract

The invention discloses a preparation method of bismuth vanadate with high (010) crystal face exposure ratio. Dissolving bismuth nitrate pentahydrate, ammonium metavanadate and citric acid in a nitric acid solution, adding ethanol and polyvinyl alcohol, coating the formed mixed solution on the surface of FTO in a spinning mode, and calcining at 450 ℃ to obtain a seed layer; dissolving bismuth nitrate pentahydrate and ammonium metavanadate in concentrated nitric acid, adding a titanium chloride solution, and adjusting the pH to 0.9 by using ammonia water to obtain a precursor solution; then immersing the seed layer in the precursor solution, and carrying out hydrothermal reaction at 180 ℃; finally, heating the product of the hydrothermal reaction to 450 ℃ for annealing to obtain the bismuth vanadate with the high (010) crystal face exposure ratio. According to the invention, the morphology regulator titanium chloride is added into the precursor solution, and the pH value of the precursor solution is regulated, so that the porous bismuth vanadate with high (010) crystal face exposure ratio is synthesized, the selectivity of the porous bismuth vanadate in photoelectrocatalysis hydrogen peroxide production is improved, and the selectivity can reach 66.5%.

Description

Preparation method of bismuth vanadate with high (010) crystal face exposure ratio
Technical Field
The invention belongs to the field of preparation of photoelectric catalytic materials, and relates to a preparation method of bismuth vanadate with a high (010) crystal face exposure ratio.
Background
Hydrogen peroxide (H) 2 O 2 ) Are widely used in industrial manufacture and as disinfectants and bleaches. Currently, about 95% of H 2 O 2 The production uses an anthraquinone process, which is a multi-step process, requiring high plant investment and large energy input. Therefore, there is a need to find H as an alternative to the anthraquinone process 2 O 2 Production processes, in particular processes which allow small-scale production under safe production conditions. Although O is reduced by hydrogenation or electrochemical processes 2 In H 2 O 2 A rapid development in synthesis has been achieved, but it is generally accepted that water is decomposed directly into H 2 And H 2 O 2 Two high value-added chemicals are production H 2 O 2 A more desirable and economically viable route. To date, researchers have discovered several metal oxides, including BiVO 4 、WO 3 、SnO 2 、TiO 2 And ZnO, optionally in the presence of HCO 3 - Or CO 3 2- Selectively producing H by water oxidation in the electrolyte of 2 O 2 . BiVO considering the influence of light collection efficiency, band edge energy and other factors 4 Due to the narrow band gap (2.4-2.5 eV), the light absorption coefficient is high (104-105 cm in the intrinsic absorption region) -1 ) And a deeper Valence Band (VB) edge, which is expected to convert solar energy to H by Water Oxidation Reaction (WOR) 2 O 2 Is desirable for the photo-anode of (1). However, in contrast to oxygen generated by 4e-WOR (1.23V vs. RHE), H 2 O 2 The generated two-electron water oxidation (2 e-WOR) purposeThe diameter (1.76v vs. rhe) is thermodynamically unfavorable. Thus, the current solar-driven WOR is relative to particle-based BiVO 4 Photo-electric anode pair H 2 O 2 The selectivity of (a) is not ideal and is usually less than 40%.
From a thermodynamic perspective, modulating the thermodynamic process of an intermediate is an effective way to modulate the selectivity to the desired product in an electrocatalytic multiple electron transfer reaction. BiVO 4 OH on the surface * Adsorption free energy (. DELTA.G) OH* ) Is considered to competitively produce O 2 And H 2 O 2 The critical bifurcation point of (a). Several successful strategies have been developed to date to modulate BiVO 4 Δ G on the surface OH* . Furthermore, biVO 4 The surface state of (a) also plays a key role in controlling the kinetics, and the passivation method affects the rate constant of charge transfer. For O 2 The 4e-WOR requirement ratio of the precipitation is used for H 2 O 2 Higher surface hole concentration of the generated 2e-WOR. The transport rate of light-induced holes can thus be delayed by using a surface passivation coating, resulting in H 2 O 2 The production activity is obviously improved. BiVO (BiVO) is caused by slow hole migration due to hole transfer to other surfaces caused by space charge separation behavior and high density of surface states 4 The (010) plane of (C) is not suitable for O 2 4e-WOR. In contrast, biVO 4 The (010) face of (a) should promote 2e-WOR by a kinetically favorable process in a kinetically-thermally favorable region.
Disclosure of Invention
The invention aims to provide a preparation method of bismuth vanadate with high (010) crystal face exposure ratio, and a bismuth vanadate crystal face regulation method for improving hydrogen peroxide yield 4 The efficiency of producing hydrogen peroxide by photoelectrochemistry can be effectively improved, and the selectivity of the hydrogen peroxide is improved.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the bismuth vanadate with the high (010) crystal face exposure ratio comprises the following specific steps:
(1) Dissolving bismuth nitrate pentahydrate, ammonium metavanadate and citric acid in a nitric acid solution, then adding ethanol and polyvinyl alcohol, stirring until the ethanol and the polyvinyl alcohol are completely dissolved, coating the obtained solution on the surface of a clean FTO (fluorine-doped tin oxide), then placing the FTO in a muffle furnace, and calcining at 450 ℃ to obtain a seed layer;
(2) Dissolving bismuth nitrate pentahydrate and ammonium metavanadate in concentrated nitric acid, then adding a titanium chloride solution, and adjusting the pH to 0.9 by using ammonia water to obtain a precursor solution;
(3) Immersing the seed layer in the precursor solution, enabling the seed layer to face downwards, and carrying out hydrothermal reaction at 180 ℃;
(4) After the reaction is finished, washing the product with water, placing the product in a muffle furnace, heating to 450 ℃, annealing, and cooling to room temperature to obtain the bismuth vanadate with high (010) crystal face exposure ratio ((010) P-BiVO) 4 )。
Preferably, in step (1), the calcination time is 2h.
Preferably, in the step (3), the hydrothermal reaction time is 12h.
Preferably, in step (4), the annealing time is 2h.
Preferably, in step (4), the temperature increase or decrease rate is 10 ℃/min.
Compared with the prior art, the invention has the following advantages:
according to the invention, the morphology regulator titanium chloride is added into the precursor solution, and the pH value of the precursor solution is regulated, so that the porous bismuth vanadate with high (010) crystal face exposure ratio is synthesized, the selectivity of the porous bismuth vanadate in photoelectrocatalysis hydrogen peroxide production is improved, and the selectivity is improved to 66.5% from the existing 40%.
Drawings
FIG. 1 shows (010) BiVO in comparative example 1 and comparative example 2 4 -1 and (010) BiVO 4 -XRD pattern of 2.
FIG. 2 shows (010) BiVO in comparative example 1 and comparative example 2 4 -1 and (010) BiVO 4 SEM picture of-2.
FIG. 3 shows (010) BiVO in comparative example 1 and comparative example 2 4 -1 and (010) BiVO 4 -2 in cross-section.
FIG. 4 shows MnO in comparative examples 1 and 2 2 Photoelectrochemistry ofAfter deposition (a) (010) BiVO 4 -1 and (b) (010) BiVO 4 -2 SEM images and energy dispersive X-ray images of the photoanode.
FIG. 5 shows (010) BiVO in comparative example 1 and comparative example 2 4 -1 and (010) BiVO 4 -2 Raman spectrum.
FIG. 6 shows P-BiVO (010) in example 1 4 SEM image of (d).
FIG. 7 shows P-BiVO (010) in example 1 4 TEM and HR-TEM images of (A).
FIG. 8 shows P-BiVO in example 1 4 SEM image of (d).
FIG. 9 shows (010) P-BiVO in example 1 4 XRD pattern of (a).
FIG. 10 shows (010) BiVO in example 1 4 -1、(010)P-BiVO 4 、P-BiVO 4 Current-voltage curve of (a).
FIG. 11 is the reaction of 1M NaHCO in example 1 3 (010) P-BiVO in electrolyte 4 And P-BiVO 4 Polarization curves of the photoanode, data were collected without illumination.
FIG. 12 is a 1M NaHCO solution used in example 1 3 (010) P-BiVO in electrolyte under AM 1.5G irradiation 4 And P-BiVO 4 PEC generation H of photoanode 2 O 2 The faraday efficiency of.
FIG. 13 is a photograph of (010) P-BiVO synthesized in comparative example 3 4 The appearance is formed when the pH value of the precursor solution is higher.
FIG. 14 shows the synthesis of (010) P-BiVO in comparative example 3 4 The appearance formed when the pH of the precursor solution is low.
Detailed Description
The present invention will be described in further detail with reference to the following examples and accompanying drawings.
Comparative example 1
Dissolving 0.3234g of bismuth nitrate pentahydrate, 0.078g of ammonium metavanadate and 0.167g of polyvinyl alcohol in a mixed solution of 1ml of concentrated nitric acid and 2ml of deionized water, violently stirring until the mixed solution is clear and transparent, spin-coating the obtained solution on the surface of a clean FTO at the speed of 1500rpm for 20s, putting the spin-coated FTO into a muffle furnace, annealing for 2h at the temperature of 450 ℃ to obtain BiVO 4 A seed layer.
Dissolving 0.1164g of bismuth nitrate pentahydrate and 0.028g of ammonium metavanadate in 1.6ml of concentrated nitric acid, adding deionized water to dilute the total volume to 60ml, pouring the obtained precursor solution into a cleaned polytetrafluoroethylene lining, and adding BiVO 4 The seed layer was immersed in the solution with the seed layer facing down. And (3) putting the polytetrafluoroethylene lining into a matched steel sleeve, screwing, putting into a forced air drying oven, and reacting for 12 hours at 180 ℃. After the reaction is finished, (010) BiVO in the polytetrafluoroethylene lining is taken out 4 And (1) putting the steel strip into a muffle furnace after being washed clean by deionized water, and annealing for 2 hours at the temperature of 450 ℃.
Comparative example 2
Dissolving 0.3234g of bismuth nitrate pentahydrate, 0.078g of ammonium metavanadate and 0.167g of polyvinyl alcohol in a mixed solution of 1ml of concentrated nitric acid and 2ml of deionized water, violently stirring until the solution is clear and transparent, spin-coating the obtained solution on the surface of clean FTO at the speed of 1500rpm for 20s, putting the spin-coated FTO into a muffle furnace, annealing for 2h at the temperature of 450 ℃ to obtain BiVO 4 A seed layer.
0.1164g of bismuth nitrate pentahydrate and 0.028g of ammonium metavanadate are dissolved in 1.6ml of concentrated nitric acid, deionized water is added to dilute the total volume to 60ml, then 0.5g of polyvinylpyrrolidone is added, and the mixture is stirred uniformly. Pouring the obtained precursor solution into a cleaned polytetrafluoroethylene lining, and adding BiVO 4 The seed layer was immersed in the solution with the seed layer facing down. And (3) putting the polytetrafluoroethylene lining into a matched steel sleeve, screwing down, putting into a forced air drying oven, and reacting for 12h at 180 ℃. After the reaction is finished, (010) BiVO in the polytetrafluoroethylene lining is taken out 4 And (2) putting the steel strip into a muffle furnace after being washed clean by deionized water, and annealing for 2 hours at the temperature of 450 ℃.
As shown in FIG. 1, (010) BiVO was determined by XRD 4 -1 and (010) BiVO 4 The crystal phases of the-2 crystals are all monoclinic BiVO 4 . In addition, with polycrystalline BiVO 4 Reference powder comparison, (010) BiVO 4 -1 and (010) BiVO 4 -2 photoanode exhibits and has a strong (010) diffraction peak, whereas (121) diffraction peakMuch weaker, this clearly indicates that (010) BiVO 4 -1 and (010) BiVO 4 -2 the photoanode is a preferential edge [010]Directionally oriented and dominated by the (010) face.
The morphology of the two photoanodes was characterized by field emission scanning electron microscopy (FE-SEM). As shown in FIG. 2, (010) BiVO 4 -1 photo-anode presents densely packed cuboid crystallites comprising symmetric (011)/(110) facets on the sides and (010) facets on the top. For (010) BiVO 4 -2 photo-anode, the crystal having a truncated rectangular pyramid morphology due to the use of PVP during the synthesis. Cross-sectional FE-SEM images show that both photoanodes are dense BiVO 4 Film composition, thickness about 450nm (FIG. 3).
By photoelectrochemical deposition of MnO 2 Deposited on (010) BiVO 4 -1 and (010) BiVO 4 -2 surfaces. As shown in FIG. 4, with (010) BiVO 4 -2 MnO formed on the surface of the photoanode 2 In sharp contrast to MnO formed by a hole oxidation process distributed on (110) facets 2 Uniformly distributed in (010) BiVO 4 -1 on the surface of the photoanode. The results show that (010) BiVO was produced under PEC conditions 4 -1 and (010) BiVO 4 -2 photo-anodes have different hole transport paths, which also correspond to the water oxidation reaction surface that occurs in the water splitting of the PEC.
As can be seen from FIG. 5, (010) BiVO 4 -1 and (010) BiVO 4 -2 the Raman spectra of the photoanode are almost identical, which means (010) BiVO 4 -1 and (010) BiVO 4 The structural defects in-2 are few or almost identical.
Example 1
2.4254g of bismuth nitrate pentahydrate, 0.5849g of ammonium metavanadate and 1.92g of citric acid were dissolved in a mixture of 5.8ml of concentrated nitric acid and 9.2ml of deionized water and stirred vigorously. Next, 3.75ml of acetic acid and 1.2g of polyvinyl alcohol were dissolved in the mixed solution and vigorously stirred until clear and transparent, the obtained solution was spin-coated on a clean FTO surface at 2000rpm for 20s, the spin-coated FTO was placed in a muffle furnace and annealed at 450 ℃ for 2h to obtain BiVO 4 A seed layer.
0.1164g of bismuth nitrate pentahydrate and 0.028g of ammonium metavanadate were dissolved in 2.0M HNO 3 (60 mL) of the aqueous solution, then 0.12mL of a titanium chloride solution (TiCl) 3 In 20-30wt.% HCl solution, solution concentration 1 mol/L) was added to the solution. The pH of the mixture was then adjusted to 0.9 with aqueous ammonia solution. Pouring the obtained precursor solution into a cleaned polytetrafluoroethylene lining, and adding BiVO 4 The seed layer was immersed in the solution with the seed layer facing down. And (3) putting the polytetrafluoroethylene lining into a matched steel sleeve, screwing down, putting into a forced air drying oven, and reacting for 12h at 180 ℃. After the reaction is finished, (010) P-BiVO in the polytetrafluoroethylene lining is taken out 4 And (3) putting the steel wire into a muffle furnace after being washed clean by deionized water, and annealing for 2 hours at the temperature of 450 ℃.
This example synthesizes (010) a faceless, porous BiVO 4 ((010)P-BiVO 4 ) Photoanode to increase active facet/electrolyte contact area and shorten hole diffusion length to further improve solar energy to H 2 O 2 The conversion efficiency of (2). Prepared (010) P-BiVO 4 The photoanode comprised a 3.5 μm thick film of nearly vertically aligned nanoplatelets, with the average size of the individual nanoplatelets being about 4 μm and the thickness being about 250nm (fig. 6a and b).
The exposed (010) face of the nanoplatelets was investigated by high resolution transmission electron microscopy (HR-TEM) and the (010) orientation was confirmed by electron diffraction (fig. 7). P-BiVO 4 The FE-SEM image of (1) is shown in FIG. 8, which contains polycrystalline nanoparticles having a size of less than 100 nm. (010) P-BiVO 4 The XRD pattern of (a) shows better orientation, the (010) diffraction peak at 2 θ =30.8 ° clearly disappears (fig. 9). This is due to the (010) plane being aligned perpendicular to the FTO substrate (commercially available FTOs are polycrystalline and dominated by the (110) plane).
Porous (010) P-BiVO 4 The photocurrent density of the photoanode was (010) BiVO 4 -1 times of the photo-anode (FIG. 10), and the photo-current density is 3.0mA/cm under the condition of 1.76V vs. RHE 2 . Although (010) P-BiVO 4 The photocurrent density of the porous bismuth vanadate (P-BiVO) is slightly lower than that of the porous bismuth vanadate (P-BiVO) with an unexposed (010) surface 4 ) But oxidation of waterTo H 2 O 2 Shows (010) P-BiVO 4 The cathode overpotential of (2) is shifted by 138mV (FIG. 11). In (010) P-BiVO 4 Production of H 2 O 2 Has a Faraday efficiency of about P-BiVO 4 3 times higher (fig. 12). (010) P-BiVO at an applied bias of 0.6 to 1.8V relative to RHE 4 To produce H 2 O 2 The Faraday efficiency of the composite material reaches 66.5 percent on average.
Comparative example 3
This comparative example is essentially the same as example 1, except that the pH is adjusted to 1.5.
Comparative example 4
This comparative example is essentially the same as example 1, except that the pH is adjusted to 0.4.
When preparing precursor solution, the pH value of the solution is opposite to the finally grown BiVO 4 The appearance is greatly influenced. As shown in FIG. 13, biVO was formed when the pH was more than 0.9 4 In contrast to fig. 5, the shape was too thick to accurately expose the (010) face. When the pH is less than 0.9, biVO is formed as shown in FIG. 14 4 The whole is thin, the shape is broken flake-shaped, the surface is incomplete, and the growth is not successful to the required shape.

Claims (1)

1. The preparation method of the bismuth vanadate with high (010) crystal face exposure ratio is characterized by comprising the following specific steps:
(1) Dissolving bismuth nitrate pentahydrate, ammonium metavanadate and citric acid in a nitric acid solution, then adding ethanol and polyvinyl alcohol, stirring until the ethanol and the polyvinyl alcohol are completely dissolved, coating the obtained solution on the surface of a clean FTO (fluorine-doped tin oxide), then placing the FTO in a muffle furnace, and calcining for 2 hours at 450 ℃ to obtain a seed layer;
(2) Dissolving bismuth nitrate pentahydrate and ammonium metavanadate in concentrated nitric acid, then adding a titanium chloride solution, and adjusting the pH to 0.9 by using ammonia water to obtain a precursor solution;
(3) Immersing the seed layer in the precursor solution, enabling the seed layer to face downwards, and carrying out hydrothermal reaction for 12 hours at 180 ℃;
(4) After the reaction is finished, the product is washed clean by water, placed in a muffle furnace, heated to 450 ℃ and annealed for 2h, cooled to room temperature, and heated or cooled at a speed of 10 ℃/min to obtain bismuth vanadate with a high (010) crystal face exposure ratio, wherein the bismuth vanadate with the high (010) crystal face exposure ratio is porous bismuth vanadate and is a vertically arranged nanosheet film which is 3.5 micrometers thick, the average size of a single nanosheet is 4 micrometers, and the thickness of the nanosheet is 250 nm.
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